Fulling and scouring compositions



material carbonizes any cellulosic material.

United States Patent:

FULLING AND SCOURING COMPOSITIONS Joseph Hunter, Brooklyn, N.Y., andMaurice J. Kelley,

Bloomfield, and William Nothum, Chatham, N.J., assignors to NopcoChemical Company, Harrison, N.J., a corporation of New Jersey NoDrawing. Application July 7, 1955 Serial No. 520,616

Claims. (Cl. 252-8.75)

This invention relates to improved surface active agents and moreparticularly to such agents which are highly useful in the fulling andscouring of woolen and worsted fabrics.

In converting raw Wool to a finished fabric a number of processing stepsare required. The first step is to subject the raw wool to a scouringprocedure to remove the wool grease, dirt and other extraneous foreignmatter 'which may have become attached to the Wool fibers. Next thescoured raw wool is subjected to a carding operation which causes thewool fibers to be aligned in a relatively parallel direction. Thereafterthe carded wool is put through a spinning operation to convert thefibers to woolen yarn. Then the yarn is woven into cloth. In thecarding, spinning and weaving operations various oily materials areusually applied to the wool to reduce or eliminate static electricityand to aid the workability 'of the fibers and the yarn by providinglubrication for the fibers and the yarn. The cloth as it comes from theweaving operation is comparatively loose, porous and thin. In order toconvert the cloth to the form in which it is used in producing woolenclothing and other customer goods the cloth must be subjected to afulling process, and immediately thereafter it is subjected to ascouring procedure to remove the lubricants employed in the carding,spinning and weaving operations. Frequently, after the fulling andscouring procedures, the cloth is subjected to a carbonizing procedureto remove any cellulosic matter which may not have been removed by theprocedure operations. This carbonizing procedure involves wetting thewoolen cloth with a dilute solution of an acid such as sulfuric acid orof a salt such as aluminum chloride and then baking the cloth which willresult in the sulfuric acid being concentrated through evaporation ofthe moisture from the dilute solution and which will result in formationby hydrochloric acid from the aqueous solution of aluminum chloride. Theconcentrated acid The carbonized material is then removed by a washingprocedure. In many cases the commercial procedure which is now used forthe production of woolen cloth involves carbonizing the cloth just priorto the fulling and scouring procedures. In those cases where the clothhas been car- 'bonized prior to the fulling and scouring operations, ithas been necessary in the past to neutralize the acid material remainingon the cloth in a separate step and then thoroughly rinse the clothbefore carrying out the fulling and scouring operations.

The fulling and scouring procedures involve first passing the thin,loose and porous woolen cloth through a series of rollers which tend tocause the fibers in the cloth to migrate and thereby become entangledwith each other thus reducing the thinness, looseness and porosity ofthe cloth. There are very small scales on the sides of Woolen fibers andthese scales tend to keep the various fibers in the cloth from pullingaway from each other. To aid in the migration of the fibers during thefulling gop'eration, it 'has'been thc 'c'us'tom in the' past to applysolutions of water-soluble soaps to the cloth prior to the fullingprocedure to help lubricate and moisten the fibers. Following thefulling operation the cloth is scoured by immersing it in water andthoroughly agitating the cloth in the water. The soap solution which hasbeen applied to the cloth for the fulling operation is dissolved in thescouring bath and serves as the detergent to wash from the cloth thelubricating oils used in the carding, spinning and weaving operations.Experience has shown that it is advantageous to have present in thefulling and scouring solutions certain amounts of soda ash, i.e. sodiumcarbonate. The use of the common water-soluble soaps in the fulling andscouring procedures has not been completely satisfactory for a number ofreasons. As is well known, ordinary watersoluble soaps have very poorresistance to hard water, which is encountered in many areas. Anotherreason is that in the scouring of the cloth following the fullingprocedure, the soaps do not rinse out of the woolen cloth as efiicientlyas desired and do not remove from the cloth with the efiiciency desiredthe lubricants used in the carding, spinning and weaving operations.Another disadvantage is the rather high labor cost in the preparation ofstock solutions of soap for use in the fulling and scouring procedure.Because of the inherent disadvantages of soaps for fulling and scouringof woolen cloth, there is a considerable demand for improved agents foruse in the fulling and scouring procedures and particularly for suchagents which will be highly stable in large concentrations of soda ash.

It is the object of this invention to provide improved compositions foruse in the fulling and scouring of woolen and worsted fabrics.

A further object of the invention is to. provide compositions for thefulling and scouring of woolen and .worsted fabrics which will readilydissolve in and which and which Will eliminate the need for separatewashing and rinsing steps following the carbonizing procedure when thatprocedure is carried out prior to the fulling and scouring procedures.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The above and other objects of the invention are accomplished byproviding compositions which are mixtures of fatty amide condensates ofthe type described hereinafter and sulfated fatty acids having arelatively high S0 content.

The compositions of the invention readily dissolve in and are highlystable in aqueous solutions containing large amounts of carbonates. Theyhave excellent detergent properties and give. very excellent resultsvwhen employed for the fulling and scouring of woolen and worsted fabricseven When the fulling and scouring are carried out immediately followingcarbonizing of the fabrics. By use of the compositions of our inventionit is possible to have sufiicient soda ash present in the fullingsolution to neutralize the acid material remaining on the carbonizedcloth plus the amount of soda ash needed for the fulling and scouringprocedures thus eliminating the separate steps of neutralizing andrinsing prior to fulling as is required in hte prior art procedures. Thecompositions of the invention are highly superior to soap for use in thefulling and scouring of woolen and worsted f brics both from a coststandpoint and because they can be employed underconditionswhere soapwill not give satisfactory results. The ingredientsem'ployed inpreparing the compositions of the invention exert a synergistic effecton each other since the compositions have a far greater degree ofdetergency than would be expected from the detergency of the individualcomponents. Because of the excellent detergent characteristics of thecompositions they are highly suitable for use for general detergentpurposes although they are primarily intended for use in the fulling andscouring of woolen and worsted fabrics.

The fatty amide condensates which are employed in preparing thecompositions of the invention are produced by reacting an alkylolaminesuch as diethanolamine, N- ethylethanolamine, diisopropanolamine,2-amino-2-methyl-l-propanol, isopropylethanolamine,trimethylolaminomethane, mo'noisopropanolamine, monoethanolamine,diglycerylamine, and similar alkylolamines or mixtures thereof with afatty acylating substance containing at least 12 carbon atoms in theacyl group. From 1.5 mols to 3 mols of alkylolamine are employed foreach equivalent of the fatty acylating substance. The fatty acylatingsubstance may be'a fatty acid or a mixture thereof, an acyl halide or anester or esters of fatty acids. Thus fatty acids such as lauric,myristic, palmitic, stearic, oleic, ricinoleic and similar acids or acylhalides, alkyl esters or glycerides thereof can be employed if desired.The preferred acylating substance is coconut oil itself or a mixture ofcoconut oil and tallow and the preferred alkylolamine is diethanolamine.Although at least 1.5 mols of alkylolamine for each equivalent of fattyacylating material is employed, it is preferred to use at least 2 molsof the alkylolamine for each equivalent of acylating agent. Since thestructure of the composition which is formed by reacting analkylo'lamine with a fatty acylating agent employing an excess of thealkylolamine has not been definitely established, the reaction productobtained is referred to herein merely as a fatty amide condensate andsuch term is used to denote the product or products obtained when theacylating substance combines with the alkylolamine with the splittingoff of water or a hydrohalide or an alcohol depending on the type ofacylating agent employed.

The sulfated fatty acid which is employed in the compositions of theinvention should have a relatively high content of S i.e. at least aboutand in most cases it is preferred that it have an S0 content of at leastabout 13% to 15%. The preferred sulfated fatty acid is sulfated oleicacid. Highly sulfated oleic acid can readily be prepared by sulfatinglow molecular weight alcohol esters of oleic acid and then saponifyingthe sulfated esters to give the free sulfated oleic acid. The sulfatedgroup on the sulfated fatty acid is neutralized with an alkali in theusual manner following the sulfation. Such a sulfation procedure is wellknown in the art and, therefore, details will not be set forth herein.If desired, some of the sulfated oleic acid may be left in the form ofits low molecular weight alcohol ester. However, in all cases the esterof the sulfated acid should be saponified to such an extent that theproduct has an acid value of at least 100. If desired, mixtures ofhighly sulfated fatty acid and sulfated fatty acid having an S0 contentof less than 10% may be employed provided the final mixture in all caseshas an average S0 content of 10% or greater. 'Likewise mixtures ofsulfated fatty acids and sulfated fatty esters having an acid valuebelow 100 may be employed with mixtures of sulfated fatty acids andsulfated fatty esters having acid values above 100 provided the acidvalue of the final mixture is at least 100. Fatty acids such asricinoleic acid can be used in place of or together with oleic acid inpreparing the highly sulfated fatty acid used for the products of theinvention.

In preparing the compositions of the invention the fatty amidecondensate and the sulfated fatty acid are employed in a ratio of from 5parts of fatty amide con- .densate to, 1 part of sulfated fatty acid toa ratio of 1 j of fatty amide condensate to..2 7 parts of sulfated fattyacid. The preferred ratio is approximately 2 parts of fatty amidecondensate to each part of sulfated fatty acid.

The products as prepared for shipment to the customer may besubstantially moisture-free although in most cases in the preparation ofthe sulfated fatty acid some moisture will be introduced into thesulfated fatty acid product during the process of its manufacture. Inmost cases it is preferred that the moisture content of the compositionsas shipped to the customer is not greater than about 79% for the obviousreasons of savings on freight, storage charges and container costs. Ifdesired, the materials can be completely anhydrous although as apractical matter it is not economical to produce them completely free ofwater. Also in most cases the anhydrous products would be pastes insteadof liquid materials. Such pastes would be more difficult for the textilemill to use than the liquid products.

In the fulling and scouring of woolen and worsted fabrics thecompositions of the invention are used to replace the water-solublesoaps employed in the conventional fulling and scouring operations. Thecompositions of the inventionare considerably superior to soap sincethey are stable under all conditions of use, ie both in hard and softwater and in alkaline and acid solutions. Considerable savings in laborare realized by the use of the compositions of the invention since thestock solutions may be quickly prepared whereas a considerable length oftime is often required for the preparation of stock solutions of soap.The actual quantities of the compositions of the invention which areemployed will vary depending upon each mills particular requirements. Inmost cases it will be found that a concentration of from 0.5% to 2%(calculated on a moisture-free basis) of the compositions in the fullingand scouring solutions is sufiicient to give very excellent results. Theamount employed does not depend upon the quantity of sodium carbonatesor sodium bicarbonate which is added to the fulling and scouringsolutions. Consequently, if the woolen or worsted fabric is carbonizedprior to fulling and scouring, it is not necessary to employ largeramounts of the compositions of the invention than when the carbonizingis done after the fulling and scouring even though sufiicient additionalsoda ash to neutralize all the acid material remaining on the carbonizedcloth is added to the fulling solution.

It has not been definitely determined just why the compositions of theinvention give results which are superior to the use of soaps and whythese compositions are exceedingly stable under both acid and alkalineconditions. It is very possible that the sulfated fatty acid and thefatty amide condensate form a stable salt or adduct which is notaffected by either acid or alkaline conditions. Regardless of the reasonfor the excellent results obtained with the compositions of theinvention, both laboratory and mill tests demonstrate quite clearly theoutstanding utility of the compositions of the invention.

In some cases pine oil is added to fulling and scouring solutions for anumber of purposes such as aiding the solutions to spread rapidlythrough the cloth, to prevent redepo'sition on the cloth of any dyesthat may be removed'from the cloth during the fulling and scouring, andto aid in removing from the cloth the lubricants applied during thecarding, spinning and weaving operations. The compositions of ourinvention are completely compatible with pine oil and may be used freelywith it.

For a fuller understanding of the nature and objects of the invention,reference may be had to the-following examples which are given-merely asfurther illustrations of the invention and are not to be construed in alimiting sense. Unless otherwise specified, all parts are given byweight.

Example I A fatty amide condensatelwas prepared by reacting 2.2 mols ofdiethanolamine with one equivalent of a fatty material composed of amixture of 75% coconut oil and tallow. To 55 parts of this fatty amidecondensate there were added 45 parts of a sulfated oleic acid having anS0 content of 13.5% and an acid value of 150. This sulfated oleic acidhad been prepared by sulfating methyl oleate and then hydrolyzing thesulfated ester to give a sulfated fatty acid product having the desiredacid value. The sulfated fatty acid contained 40% water. The compositionprepared by mixing the fatty amide condensate with the sulfated oleicacid was highly stable in solutions containing relatively large amountsof carbonates. In addition the product was a highly effective foamingagent and detergent.

To show the synergistic effect which the ingredients have on each otherwith respect to foaming properties, the well known Ross-Miles foam testwas carried out on a 0.5% active solution of each of the ingredients andof the blended composition in tap water at 25 C. The initial foam of thefatty amide condensate was 180 mm. After five minutes the foam was 150mm. The initial foam of the sulfated acid was 175 mm. but after fiveminutes it was 0 mm. The blend of the fatty amide condensate and thesulfated acid had an initial foam of 255 mm. and after five minutes hada foam of 215 mm. thus unequivocally demonstrating that the ingredientshad a highly synergistic effect on each other with respect to their foamproducing properties.

A similar test with respect to the synergistic effect of the ingredientson each other as far as detergency is con cerned was carried out. Thistest showed that there is avery high degree of synergism with respect tothe detergent properties. This test was carried out in an AtlasLaunder-O-Meter using a 0.15% active solution of the ingredients and ofthe blended composition in each case in tap water at 120 F. and usingstandard soiled woolen cloth supplied by the United States TestingCompany. The fatty amide condensate had a detergency of 53% whereas thesulfated fatty acid had a detergency of 0%. The blend of the twoingredients, however, had a detergency of 54%.

The effectiveness of the blended composition as a fulling and scouringagent was tested in a textile mill on various types of woolen fabricsranging from a fine worsted containing very little oil (1%) to a cheaperconstruction, i.e. 13 /2 ounce worsted with considerable oil on it. Inthe tests 27 pounds of the blended composition were mixed with 60 poundsof soda ash and sufficient water to give a total of 375 gallons. Theresulting fulling solution was metered directly on the fabric using aweight of the fulling solution approximately equal to the weight of thefabric being treated. Approximately the same amount of time was employedfor the fulling process as with conventional fulling agents. Followingthe fulling procedure the fabrics were then washed in the usual mannerexcept that the conventional detergents employed in the scouring bathwere replaced with equivalent amounts of the compositions of thisexample. The resulting fabrics had a very excellent hand, appearance andodor and a very low content of material extractable with ethyl ether andethyl alcohol.

Example II Another composition of the invention was prepared in the samemanner as the product of Example I except that the fatty amidecondensate was prepared from 2.2 equivalents of diethanolamine and oneequivalent of coconut oil. When this fatty amide condensate was blendedwith the sulfated fatty acid employed in Example I using the sameproportions as in Example I a highly satisfactory fulling and scouringcomposition was obtained.

Example III Another excellent product was prepared employing as thefatty amide condensate a product prepared by reacting 2.2mols-ofdiethanolamine with one mol of coconut fatty acids.

Example IV Another product of the invention was prepared in the samemanner as in Example I except that the fatty amide condensate wasprepared from 2 mols of diethanolamine and one mol of lauric acid.

Example V The product of this example was similar to that of theprevious examples except that the fatty amide condensate was preparedfrom 2 mols of diethanolamine and one mol of myristic acid.

Example VI Another product of the invention was prepared as in theprevious examples except that the fatty amide condensate was preparedfrom 2 mols of diethanolamine and one mol of palmitic acid.

Example VII A product wherein the fatty amide condensate was preparedfrom a mixture of alkylolarnines was prepared by reacting one equivalentof lauric acid with a mixture of 1 /2 mols of diethanolamine andone-half mol of diisopropanolarnine. This fatty amidle condensate wasblended with the sulfated fatty acid employed in Example I using thesame ratios as in Examplel to give a highly effective fulling andscouring composition.

Example VIII In this example the fatty amide condensate was prepared byreacting one equivalent of coconut fatty acids with a mixture of 1 /2mols of diethanolamine and onehalf mol of monoisopropanolamine. Theblended compositions prepared from this fatty amide condensate and thesulfated oleic acid of Example I using the same ratios as in Example Igave a very excellent fulling and scouring composition.

Example IX 18.7 parts of the fatty amide condensate employed in ExampleI were mixed with 9.7 parts of a sulfated oleic acid having an acidvalue of 150 and an S0 content of approximately 9%, 9.1 parts of asulfated oleic acid having an acid value of 70 and an S0 content of 14%,2.9 parts of pine oil and 59.6 parts of water. The sulfated oleic acidhaving the content of approximately 9% contained about 30% water and thesulfated oleic acid having an S0 content of about 14% contained about44% water. Thus the final composition had a Water content ofapproximately 67%. This product had very excellent stability insolutions containing relatively large amounts of carbonates and hadexcellent fulling and scouring properties when employed in full scaleplant tests. The product of the example was employed in a fullingsolution at a concentration of 5 ounces per gallon, i.e. approximately1.7 ounces per gallon on an active basis. The fulling solution alsocontained 1 /2 ounces of soda ash, 1 /2 ounces of sodium bicarbonate andA ounce of a commercial sequestering agent. Very excellent results wereobtained in the fulling of the woolen fabrics with this solution usingthe same fulling time as when soap was employed as the fullingdetergent. The sudsing qualities of the fulling solution were farsuperior to the fulling solutions prepared using soap as the detergentand in addition there was a great saving in labor in the preparation ofthe fulling solution as compared to the preparation of the solution whensoap is used as the detergent. It was found that the fabric after itcame out of the washing bath was completely free of any carbontetrachloride-soluble material whereas when soap was employed as thedetergent in fulling and scouring it wasflnot possible to obtain afabric completely free of carbon tetrachloride-soluble material.

Example X Another fulling and scouring composition of the invention wasprepared by mixing 16.8 parts of the fatty amide condensate of Example Iwith 12.8 parts of the sulfated oleic acid of Example IX which contained9% S 8.0 parts of the sulfated oleic acid of Example 1X which contained14% S0 2.9 parts of pine oil and 59.5 parts of water. The resultingcomposition was a very excellent fulling and scouring composition andhad the same excellent qualities as the products of the previousexamples.

Having described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A composition consisting essentially of (a) a fatty amide condensateprepared by reacting from one and one-half mols to three mols of analkylolamine with one equivalent of a fatty acylating substance selectedfrom the group consisting of fatty acids, acyl halides, esters of fattyacids and mixtures thereof having a fatty chain length of at leasttwelve carbon atoms and (b) a sulfated fatty acid having an acid valueof at least 100 and an S0 content of at least said fatty amidecondensate and said sulfated fatty acid being present in a ratio of fromabout five parts of fatty amide condensate to one part of sulfated fattyacid to about one part of fatty amide condensate to two parts ofsulfated fatty acid.

2. The composition of claim 1 wherein the fatty acylating substance is amixture of coconut oil and tallow.

3. The composition of claim 1 wherein the fatty amide condensate isprepared from one equivalent of the fatty acylating substance and abouttwo equivalents of alkylolamine.

4. The composition of claim 3 wherein the fatty acylating substance is amixture of coconut oil and tallow.

5. The composition of claim 3 wherein the alkylolamine isdiethanolamine.

6. The composition of claim 3 wherein the sulfated fatty acid materialis a mixture of sulfated methyl oleate and sulfated oleic acid having anacid value of at least about and an S0 content of at least about 13%.

7. The composition of claim 4 wherein the alkylolamine isdiethanolamine.

8. The composition of claim 4 wherein the sulfated fatty acid materialis a mixture of sulfated methyl oleate and sulfated oleic acid having anacid value of at least about 150 and an S0 content of at least about13%.

9. The composition of claim 5 wherein the sulfated fatty acid materialis a mixture of sulfated methyl oleate and sulfated oleic acid having anacid value ofat least about 150 and an $0 content of at least about 13%.

10. The composition of claim 7 wherein the sulfated fatty acid materialis a mixture of sulfated methyl oleate and sulfated oleic acid having anacid value of at least about 150 and an S0 content of at least about13%.

References Cited in the file of this patent UNITED STATES PATENTS2,245,412 Pilgrim June 10, 1941 2,483,253 Young Sept. 27, 1949 FOREIGNPATENTS 665,475 Great Britain Jan. 23, 1952

1. A COMPOSITION CONSISTING ESSENTIALLY OF (A) A FATTY AMIDE CONDENSATEPREPARED BY REACTING FROM ONE AND ONE-HALF MOLS TO THREE MOLS OF ANALKYLOLAMINE WITH ONE EQUIVALENT OF A FATTY ACYLATING SUBSTANCE SELECTEDFROM THE GROUP CONSISTING OF FATTY ACIDS, ACYL HALIDES, ESTERS OF FATTYACIDS AND MIXTURES THEREOF HAVING A FATTY CHAIN LENGTH OF AT LEASTTWELVE CARBON ATOMS AND (B) A SULFATED FATTY ACID HAVING AN ACID VALUEOF AT LEAST 100 AND AN SO3 CONTENT OF AT LEAST 10%, SAID FATTY AMIDECONDENSATE AND SAID SULFATED FATTY ACID BEING PRESENT IN A RATIO OF FROMABOUT FIVE PARTS OF FATTY AMIDE CONDENSATE TO ONE PART OF SULFATED FATTYACID TO ABOUT ONE PART OF FATTY AMIDE CONDENSATE TO TWO PARTS OFSULFATED FATTY ACID.